EP1542795A2 - Catalytic method of producing mercaptans from thioethers - Google Patents

Catalytic method of producing mercaptans from thioethers

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Publication number
EP1542795A2
EP1542795A2 EP03773807A EP03773807A EP1542795A2 EP 1542795 A2 EP1542795 A2 EP 1542795A2 EP 03773807 A EP03773807 A EP 03773807A EP 03773807 A EP03773807 A EP 03773807A EP 1542795 A2 EP1542795 A2 EP 1542795A2
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Prior art keywords
strong acid
weight
metal
hydrogen
catalytic composition
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EP03773807A
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German (de)
French (fr)
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EP1542795B1 (en
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Georges Fremy
Nadine Essayem
Michel Lacroix
Elodie Zausa
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Arkema France SA
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Arkema SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B45/00—Formation or introduction of functional groups containing sulfur
    • C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
    • C07C321/04—Thiols having mercapto groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton

Definitions

  • the present invention relates to the field of mercaptans (also called thiols) and more particularly relates to a catalytic process for the manufacture of mercaptans from thioethers and hydrogen sulfide, in the presence of hydrogen and a specific catalyst.
  • mercaptans also called thiols
  • the present invention relates to the field of mercaptans (also called thiols) and more particularly relates to a catalytic process for the manufacture of mercaptans from thioethers and hydrogen sulfide, in the presence of hydrogen and a specific catalyst.
  • the thioethers obtained as by-products during the manufacture of mercaptans are generally not of commercial interest.
  • US Pat. No. 4,005,149 thus describes the production of mercaptans (or thiols) by reaction of H 2 S with organic sulfides (another name of thioethers) in the presence, as catalyst, of a sulfide of a group VI metal and / or a group VIII metal, in particular a cobalt and molybdenum sulfide (Co / Mo) impregnated on an alumina support.
  • Carbon disulfide CS 2 is added to the reaction mixture to improve the conversion of organic sulfide to mercaptan.
  • US Patent 4,059,636 describes the use of a solid catalyst comprising a 12-phosphotungstic acid supported on alumina.
  • This catalyst compared to a usual catalyst such as molybdenum and cobalt supported on alumina (CoMo / Al 2 O 3 ) has the effect of a higher conversion and selectivity when it is used in the sulfhydrolysis reaction, and this for a lower reaction temperature.
  • a usual catalyst such as molybdenum and cobalt supported on alumina (CoMo / Al 2 O 3 )
  • MoMo / Al 2 O 3 molybdenum and cobalt supported on alumina
  • it may require the presence of carbon sulfide CS 2 as a promoter. No indication is given about the stability over time of this catalytic system.
  • a solid catalyst comprising a 12-phosphotungstic acid supported on silica is also described by US patent 5,420,092. This document teaches, more generally, the use of a heteropolyacid combined with a metal of the NUI group, but in the distant field of the isomerization of paraffins.
  • a new catalytic process has now been found for the preparation of mercaptans from thioethers and hydrogen sulphide which uses hydrogen in the reaction flow and a specific catalyst. It has the advantage of using lower temperatures, to obtain with a good yield of. high purity mercaptans, and maintain the high activity of the catalyst over time.
  • the subject of the invention is therefore a process for the manufacture of a mercaptan from a thioether and hydrogen sulfide, characterized in that it is carried out in the presence of hydrogen and of a catalytic composition comprising a strong acid and at least one metal belonging to the NUI group of the periodic table.
  • the strong acid which can be used in the catalytic composition is taken from the group comprising: - (a) one or more heteropolyacid (s) chosen from:
  • n is an integer representing the number of molecules of water of crystallization, and (being a commercial product) is generally between 0 and 30, preferably between 6 and 20;
  • the heteropolyacid (i) is generally obtained by the condensation of 2 or more different oxoacids, such as phosphoric acid, silicic acid or tungstic acid. It is soluble in water or in a polar organic solvent.
  • the compound of formula: H 3 PW ⁇ 2 O 4 o, nH 2 O is known by the name 12-phosphotungstic or 12-tungstophosphoric acid, and is available commercially.
  • the compound of formula: H 4 SiW ⁇ 2 O 4 o, nH 2 O is known under the name 12-tungstosilicic or 12-silicotungstic acid, and is also commercially available.
  • the compound of formula: H 6 P 2 Wj 8 ⁇ 6 , nH 2 O can be prepared according to the procedure described in the following reference: AP Ginsberg, Inorganic Synthesis, Nol 27, Published by J. Wiley & sons (1990) pages 105-107.
  • the heteropolyacid (ii) is a salt obtained by partial substitution of one or more protons of the heteropolyacid (i) with the corresponding cation. It is clear to a person skilled in the art that such a substitution cannot be total, otherwise the acidity would be lost.
  • Such a salt is prepared from a solution of the heteropolyacid (i) to which is added the desired amount of the alkali or ammonium precursor. The preferred precursor is the corresponding chloride or carbonate.
  • the precipitated salt is separated and then dried under mild conditions, preferably by centrifugation followed by lyophilization.
  • the sulfated zirconia (b) is prepared by impregnation of sulfuric acid on a zirconium oxide support in accordance with the process described in the reference: FR Chen, G. Coudurier, JF Joly and JC Védrine, J. Catal., 143 ( 1993) page 617.
  • the tungsten zirconia (c) is prepared by impregnation of tungsten oxide on a zirconium oxide support, according to the process described in the patent Soled et al. US 5113034.
  • the catalyst used in it comprises as strong acid a heteropolyacid (ii), or one of the compounds (b), (c), (d) or (e).
  • This variant is preferred because, because of the specific surface properties of such a strong acid, the latter is generally suitable as a support. It is therefore not necessary in this case to deposit the strong acid on a support.
  • the catalytic composition includes:
  • the catalyst used comprises, as a strong acid, a heteropolyacid (i). This variant is preferred because of a particularly advantageous activity of the catalyst in the sulfhydrolysis reaction.
  • the catalytic composition in this case comprises: from 10 to 60%, and preferably from 25 to 50% by weight of strong acid,
  • a support chosen from silica SiO 2 , alumina Al 2 O 3 , titanium oxide TiO 2 , zirconia ZrO 2 or activated carbon .
  • the strong acid used in the catalyst is 12-phosphotungstic acid, preferably impregnated on silica.
  • the metal or metals belonging to group VIII of the periodic classification generally included in the catalytic composition used are chosen from in particular iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium , platinum. It is preferred to use a group VIII metal chosen from palladium, ruthenium and platinum, and very particularly palladium.
  • a particularly preferred catalytic composition is that comprising approximately: 40% by weight of 12-phosphotungstic acid, 1% of palladium and 59% of silica.
  • the catalytic composition used in the process according to the invention can be generally prepared in the following manner.
  • the purpose of the heat treatment in step (1) is to desorb the water possibly adsorbed in the pores of the support.
  • the expression “acid precursor” is understood to mean a compound giving an aqueous cationic complex. or anionic of said metal.
  • acid precursor is understood to mean a compound giving an aqueous cationic complex. or anionic of said metal.
  • exemplary such compounds are, in the case of platinum: platinum hydroxide tetramine, platinum tetramine chloride, dinitrodiamine-platinum (II), or alternatively, in the case of palladium, palladium chloride , Pd (NH 3 ) 4 Cl 2 , (NH 4 ) 2 (PdCl 4 ).
  • hexachloroplatinic acid also called hydrogen hexachloroplatinate (IV)
  • ammonium tetrachloroplatinate (II) ammonium hexachloroplatinate (IV).
  • acid precursors is given previously for purely illustrative purposes, without limiting the compounds which can be used as acid precursor by those skilled in the art.
  • step (3) the drying can for example be carried out by heating the impregnated support, optionally under vacuum, to a temperature generally between room temperature and 120 ° C, for a time ranging from 30 minutes to 5 hours.
  • the treatment with H 2 of step (4) is advantageously carried out on the catalyst when the latter is placed in the sulfhydrolysis reactor, and has the aim of reducing the acid precursor to the metal of group VIII.
  • the catalyst used comprises as strong acid a heteropolyacid (ii), or one of the compounds (b), (c), (d) or (e), it can be prepared according to the same process, using except that the heat treatment is not compulsory, and must even be removed or modified according to the characteristics of the support.
  • the catalytic composition described above is used in the process for manufacturing mercaptan according to the invention which comprises the reaction of hydrogen sulfide (H 2 S) on a thioether in the presence of hydrogen.
  • This process is carried out in the gas phase, insofar as the temperature and pressure conditions used are such that the reactants and the products are in the gaseous state.
  • the hydrogen introduced into the process in an amount corresponding to a H 2 S / H 2 molar ratio of between 10 and 200, preferably between 50 and 100.
  • the thioether (or organic sulfide) used as starting reagent has the general formula:
  • R and R' represent an alkyl radical of 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, linear or branched, or else a cycloalkyl radical of .3 with 7 carbon atoms.
  • the thioether even more preferably used is diethylsulfide (or ethylthioether).
  • the sulfhydrolysis reaction leads in this case to ethylmercaptan (or ethanethiol).
  • the hydrogen sulfide is introduced into the process in an amount sufficient to obtain the conversion of the organic sulfide.
  • this quantity corresponds to a H 2 S / thioether molar ratio of between 1 and 40, preferably between 2 and 30, even more preferably between 2 and 10.
  • the reagents described above are brought into contact, in the presence of a charge of the catalytic composition defined above, in a suitable reaction zone, under reaction conditions suitable for producing the desired thiol.
  • the reaction temperature varies depending on the thioether used and the degree of conversion desired, but is generally within a range of between 50 and 350 ° C, preferably between 150 and 250 ° C.
  • the pressure at which the reaction is carried out also varies within wide limits. Usually, it is between atmospheric pressure and 20 bars, preferably between 10 and 15 bars.
  • the contact time is generally between 1 and 50 s, preferably between 10 and 30 s.
  • the thioether used in the process according to the invention may be the by-product obtained in a process for the manufacture of thiol by the addition of hydrogen sulfide on an alcohol or on an olefin, in the presence of a catalyst and / or by photochemical activation. In this variant of the process, it is thus possible to advantageously develop said by-product.
  • HPW corresponds to 12-phosphotungstic acid of formula H 3 PW ⁇ 2 O 40 , nH 2 O.
  • an aqueous solution comprising 6 g of PdCl 2 and 140 g of HPW (weight expressed in anhydrous acid equivalent, ie with n equal to 0).
  • An amorphous silica having a specific surface (or BET) of 315 is used as catalyst support a pore diameter of the order of 12 to 14 nm and a pore volume of 1.6 cm. g " .
  • This support is previously treated under vacuum at a temperature of 100 ° C. The impregnation of the solution previously obtained on the support thus treated is carried out under vacuum by suction. Once the solution has been impregnated, the mixture is stirred for 1 hour at atmospheric pressure.
  • the product obtained is dried under vacuum, at ambient temperature, then is subjected to a treatment with hydrogen at a temperature of 230 ° C. aimed at reducing the palladium.
  • the catalyst obtained consists of 59% by weight of SiO 2 , 1% by weight of Pd and 40% by weight of HPW.
  • Example 2 Preparation of ethyl mercaptan (CH 3 CH 2 -SH) from diethyl sulfide (CH 3 CH 2 -S-CH 2 CH 3 ):
  • a 25 mm diameter tubular reactor using a useful capacity of 200 ml charged with 200 ml of the catalytic composition prepared according to Example 1 is used.
  • H 2 S i.e. 5 moles
  • H 2 0.8 g of H 2 (i.e. 0.08 moles).
  • the pressure in the reactor is maintained at 15 bars and the temperature is fixed at
  • Example 2 is repeated, continuing the sulfhydrolysis reaction for 6 days with the same charge of catalytic composition, and proceeding periodically (as a function of the time expressed in days) to measure the conversion of diethyl sulfide (DES).
  • DES diethyl sulfide
  • Table 1 shows that the catalytic system prepared in Example 1 and used in the presence of hydrogen according to the process of the invention has good stability over time.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Process for obtaining a mercaptan from a thioether and hydrogen sulfide, carried out in the presence of hydrogen and a catalytic composition comprising a strong acid and a group VIII metal.

Description

PROCEDE CATALYTIQUE DE FABRICATION DE MERCAPTANS A PARTIR DE THIOETHERS CATALYTIC PROCESS FOR THE MANUFACTURE OF MERCAPTANS FROM THIOETHERS
La présente invention concerne le domaine des mercaptans (encore appelés thiols) et a plus particulièrement pour objet un procédé catalytique pour la fabrication de mercaptans à partir de thioéthers et d'hydrogène sulfuré, en présence d'hydrogène et d'un catalyseur spécifique.The present invention relates to the field of mercaptans (also called thiols) and more particularly relates to a catalytic process for the manufacture of mercaptans from thioethers and hydrogen sulfide, in the presence of hydrogen and a specific catalyst.
L'intérêt industriel des mercaptans ou thiols fait que de nombreux travaux ont été effectués en vue de la mise au point de la fabrication de ces composés. On connaît notamment un procédé largement employé qui met en oeuvre la réaction de l'hydrogène sulfuré avec un alcool ou une oléfine. Dans une telle réaction, on obtient en particulier comme sous-produit un ou plusieurs thioéthers qui résultent de réactions secondaires, et principalement de la réaction du mercaptan (formé dans la réaction principale) sur le réactif de départ c'est-à-dire soit l' alcool, soit l' oléfine, selon le procédé utilisé.The industrial interest of mercaptans or thiols means that numerous works have been carried out with a view to perfecting the manufacture of these compounds. In particular, a widely used process is known which uses the reaction of hydrogen sulfide with an alcohol or an olefin. In such a reaction, one obtains in particular as a by-product one or more thioethers which result from side reactions, and mainly from the reaction of the mercaptan (formed in the main reaction) on the starting reagent, that is to say either alcohol, or olefin, according to the process used.
Les thioéthers obtenus en tant que sous-produits lors de la fabrication de mercaptans n'ont généralement pas d'intérêt commercial.The thioethers obtained as by-products during the manufacture of mercaptans are generally not of commercial interest.
Des méthodes de conversion de ces thioéthers en vue de leur valorisation ont été proposées, visant à les transformer en mercaptans par réaction avec l'hydrogène sulfuré (H2S) en présence de différents catalyseurs, réaction dite de sulfhydrolyse.Methods of converting these thioethers with a view to their valorization have been proposed, aiming to transform them into mercaptans by reaction with hydrogen sulfide (H 2 S) in the presence of different catalysts, a reaction known as sulfhydrolysis.
Les procédés existants de sulfhydrolyse mettent en œuvre cette réaction sous pression en utilisant un flux réactionnel constitué exclusivement d'H2S et de thioether en différentes proportions, en présence de différents systèmes catalytiques.Existing sulfhydrolysis processes implement this reaction under pressure using a reaction flow consisting exclusively of H 2 S and thioether in different proportions, in the presence of different catalytic systems.
Le brevet US 4,005,149 décrit ainsi l'obtention de mercaptans (ou thiols) par réaction de l'H2S sur des sulfures organiques (autre dénomination des thioéthers) en présence, comme catalyseur, d'un sulfure d'un métal du groupe VI et/ou d'un métal du groupe VIII, notamment d'un sulfure de cobalt et de molybdène (Co/Mo) imprégné sur un support d'alumine. Du disulfure de carbone CS2 est ajouté au mélange réactionnel pour améliorer la conversion du sulfure organique en mercaptan. Dans le brevet US 4,396,778 est décrit un procédé en phase vapeur de préparation d'alkyl mercaptans à haut poids moléculaire Cι-C18 en utilisant comme catalyseur une zéolithe à larges pores modifiée par du potassium ou du sodium. La réaction est menée à une température élevée, supérieure à 290°C. Les brevets US 2,829,171 et US 3,081,353 décrivent la synthèse de mercaptans plus légers tel le méthyl mercaptan en présence d'alumine activée comme catalyseur. Les températures de réaction mises en œuvre dans ces procédés sont élevées. Des résines échangeuses d'ions fortement acides telles que décrites dans le brevet US 4,927,972 sont des catalyseurs également employés dans les procédés de sulfhydrolyse de thioéthers, mais elles conduisent généralement à un faible rendement.US Pat. No. 4,005,149 thus describes the production of mercaptans (or thiols) by reaction of H 2 S with organic sulfides (another name of thioethers) in the presence, as catalyst, of a sulfide of a group VI metal and / or a group VIII metal, in particular a cobalt and molybdenum sulfide (Co / Mo) impregnated on an alumina support. Carbon disulfide CS 2 is added to the reaction mixture to improve the conversion of organic sulfide to mercaptan. In US patent 4,396,778 is described a vapor phase process for the preparation of high molecular weight Cι-C 18 alkyl mercaptans using as catalyst a large pore zeolite modified with potassium or sodium. The reaction is carried out at an elevated temperature above 290 ° C. US patents 2,829,171 and US 3,081,353 describe the synthesis of lighter mercaptans such as methyl mercaptan in the presence of activated alumina as catalyst. The reaction temperatures used in these processes are high. Strongly acid ion exchange resins as described in US Pat. No. 4,927,972 are catalysts also used in the sulfhydrolysis processes of thioethers, but they generally lead to a low yield.
Le brevet US 4,059,636 décrit l'utilisation d'un catalyseur solide comprenant un acide 12-phosphotungstique supporté sur alumine. Ce catalyseur, comparé à un catalyseur usuel tel qu'un molybdène et cobalt supporté sur alumine (CoMo/Al2O3) a pour effet une conversion et une sélectivité plus élevées quand il est mis en oeuvre dans la réaction de sulfhydrolyse, et ce pour une température de réaction plus faible. Il peut toutefois nécessiter la présence de sulfure de carbone CS2 comme promoteur. Aucune indication n'est donnée au sujet de la stabilité dans le temps de ce système catalytique.US Patent 4,059,636 describes the use of a solid catalyst comprising a 12-phosphotungstic acid supported on alumina. This catalyst, compared to a usual catalyst such as molybdenum and cobalt supported on alumina (CoMo / Al 2 O 3 ) has the effect of a higher conversion and selectivity when it is used in the sulfhydrolysis reaction, and this for a lower reaction temperature. However, it may require the presence of carbon sulfide CS 2 as a promoter. No indication is given about the stability over time of this catalytic system.
Un catalyseur solide comprenant un acide 12-phosphotungstique supporté sur silice est également décrit par le brevet US 5,420,092. Ce document enseigne, plus généralement, la mise en oeuvre d' un hétéropolyacide combiné à un métal du groupe NUI, mais dans le domaine éloigné de l'isomérisation des paraffines.A solid catalyst comprising a 12-phosphotungstic acid supported on silica is also described by US patent 5,420,092. This document teaches, more generally, the use of a heteropolyacid combined with a metal of the NUI group, but in the distant field of the isomerization of paraffins.
Il a maintenant été trouvé un nouveau procédé catalytique pour la préparation de mercaptans à partir de thioéthers et d'hydrogène sulfuré qui met en oeuvre de l'hydrogène dans le flux réactionnel et un catalyseur spécifique. Il présente l'avantage de recourir à des températures plus basses,, d'obtenir avec un bon rendement des. mercaptans de grande pureté, et de maintenir l'activité élevée du catalyseur au cours du temps.A new catalytic process has now been found for the preparation of mercaptans from thioethers and hydrogen sulphide which uses hydrogen in the reaction flow and a specific catalyst. It has the advantage of using lower temperatures, to obtain with a good yield of. high purity mercaptans, and maintain the high activity of the catalyst over time.
L'invention a donc pour objet un procédé de fabrication d'un mercaptan à partir d'un thioether et d'hydrogène sulfuré, caractérisé en ce qu'il est effectué en présence d'hydrogène et d'une composition catalytique comprenant un acide fort et au moins un métal appartenant au groupe NUI de la classification périodique.The subject of the invention is therefore a process for the manufacture of a mercaptan from a thioether and hydrogen sulfide, characterized in that it is carried out in the presence of hydrogen and of a catalytic composition comprising a strong acid and at least one metal belonging to the NUI group of the periodic table.
La combinaison de l'hydrogène avec cette composition catalytique permet de stabiliser l'activité du catalyseur dans le temps à un niveau élevé et ceci à relativement basse température. Ce résultat est d'autant plus surprenant qu'il est obtenu dans un milieu sulfurant, connu pour empoisonner les sites actifs des catalyseurs.The combination of hydrogen with this catalytic composition makes it possible to stabilize the activity of the catalyst over time at a high level and this at relatively low temperature. This result is all the more surprising since it is obtained in a sulfurizing medium, known to poison the active sites of the catalysts.
L'acide fort utilisable dans la composition catalytique est pris dans le groupe comprenant : - (a) un ou plusieurs hétéropolyacide(s) choisi(s) parmi :The strong acid which can be used in the catalytic composition is taken from the group comprising: - (a) one or more heteropolyacid (s) chosen from:
- (i) un composé de formules : H3PWι2O_ιo,nH2O, ou H6P2Wi8θ62,nH2O dans lesquelles n est un nombre entier représentant le nombre de molécules d'eau de cristallisation, et (s'agissant d'un produit commercial) est généralement compris entre 0 et 30, de préférence entre 6 et 20 ;- (i) a compound of formulas: H 3 PWι 2 O_ιo, nH 2 O, or H 6 P 2 Wi 8 θ 62 , nH 2 O in which n is an integer representing the number of molecules of water of crystallization, and (being a commercial product) is generally between 0 and 30, preferably between 6 and 20;
- (ii) un sel de potassium, rubidium, césium ou d'ammonium d'au moins un composé (i) ou un mélange de tels sels ;- (ii) a potassium, rubidium, cesium or ammonium salt of at least one compound (i) or a mixture of such salts;
- (b) une zircone sulfatée,- (b) a sulfated zirconia,
- (c) une zircone tungstée, - (d) une zéolithe, et- (c) a tungsten zirconia, - (d) a zeolite, and
- (e) une résine cationique.- (e) a cationic resin.
L' hétéropolyacide (i) est généralement obtenu par la condensation de 2 ou plus oxoacides différents, tels que l'acide phosphorique, l'acide silicique ou l'acide tungstique. Il est soluble dans l'eau ou dans un solvant organique polaire. Le composé de formule : H3PWι2O4o,nH2O est connu sous la dénomination d'acide 12- phosphotungstique ou 12-tungstophosphorique, et est disponible dans le commerce. Le composé de formule : H4SiWι2O4o,nH2O est connu sous le nom d'acide 12- tungstosilicique ou 12-silicotungstique, et est également disponible dans le commerce. Le composé de formule : H6P2Wj8θ6 ,nH2O peut être préparé selon le mode opératoire décrit dans la référence suivante : A. P. Ginsberg, Inorganic Synthesis, Nol 27, Published by J. Wiley & sons (1990) pages 105-107.The heteropolyacid (i) is generally obtained by the condensation of 2 or more different oxoacids, such as phosphoric acid, silicic acid or tungstic acid. It is soluble in water or in a polar organic solvent. The compound of formula: H 3 PWι 2 O 4 o, nH 2 O is known by the name 12-phosphotungstic or 12-tungstophosphoric acid, and is available commercially. The compound of formula: H 4 SiWι 2 O 4 o, nH 2 O is known under the name 12-tungstosilicic or 12-silicotungstic acid, and is also commercially available. The compound of formula: H 6 P 2 Wj 8 θ 6 , nH 2 O can be prepared according to the procedure described in the following reference: AP Ginsberg, Inorganic Synthesis, Nol 27, Published by J. Wiley & sons (1990) pages 105-107.
L'hétéropolyacide (ii) est un sel obtenu par substitution partielle d'un ou plusieurs protons de l'hétéropolyacide (i) par le cation correspondant. Il est clair pour l'homme du métier qu'une telle substitution ne peut être totale, sans quoi l'acidité serait perdue. Un tel sel est préparé à partir d'une solution de l'hétéropolyacide (i) à laquelle est ajoutée la quantité souhaitée du précurseur de l'alcalin ou de l'ammonium. Le précurseur préféré est le chlorure ou le carbonate correspondant. Le sel précipité est séparé, puis séché dans des conditions douces, de préférence par centrifugation suivie d'une lyophilisation. On peut citer comme référence: N. Essayem, G. Coudurier, M. Fournier, J.C. Védrine, Catal. Lett., 34 (1995) pages 224-225.The heteropolyacid (ii) is a salt obtained by partial substitution of one or more protons of the heteropolyacid (i) with the corresponding cation. It is clear to a person skilled in the art that such a substitution cannot be total, otherwise the acidity would be lost. Such a salt is prepared from a solution of the heteropolyacid (i) to which is added the desired amount of the alkali or ammonium precursor. The preferred precursor is the corresponding chloride or carbonate. The precipitated salt is separated and then dried under mild conditions, preferably by centrifugation followed by lyophilization. As a reference, we can cite: N. Essayem, G. Coudurier, M. Fournier, JC Védrine, Catal. Lett., 34 (1995) pages 224-225.
La zircone sulfatée (b) est préparée par imprégnation d'acide sulfurique sur un support d'oxyde de zirconium conformément au procédé décrit dans la référence : F. R. Chen, G. Coudurier, J-F Joly and J.C. Védrine, J. Catal., 143 (1993) page 617.The sulfated zirconia (b) is prepared by impregnation of sulfuric acid on a zirconium oxide support in accordance with the process described in the reference: FR Chen, G. Coudurier, JF Joly and JC Védrine, J. Catal., 143 ( 1993) page 617.
La zircone tungstée (c) est préparée par imprégnation d'oxyde de tungstène sur un support d'oxyde de zirconium, conformément au procédé décrit dans le brevet Soled et al. US 5113034.The tungsten zirconia (c) is prepared by impregnation of tungsten oxide on a zirconium oxide support, according to the process described in the patent Soled et al. US 5113034.
Selon une première variante de réalisation du procédé selon l'invention, le catalyseur mis en oeuvre dans celui-ci comprend comme acide fort un hétéropolyacide (ii), ou l'un des composés (b), (c), (d) ou (e). Cette variante est préférée car, en raison des propriétés de surface spécifique d'un tel acide fort, ce dernier convient généralement comme support. Il n'est donc pas dans ce cas nécessaire de déposer l'acide fort sur un support. La composition catalytique comprend dans ce cas :According to a first alternative embodiment of the process according to the invention, the catalyst used in it comprises as strong acid a heteropolyacid (ii), or one of the compounds (b), (c), (d) or (e). This variant is preferred because, because of the specific surface properties of such a strong acid, the latter is generally suitable as a support. It is therefore not necessary in this case to deposit the strong acid on a support. In this case, the catalytic composition includes:
- de 90 à 99,9 %, de préférence de 98,5 à 99,5 %, en poids d'acide fort, etfrom 90 to 99.9%, preferably from 98.5 to 99.5%, by weight of strong acid, and
- de 0,01 à 10 %, de préférence de 0,05 à 1,5 % en poids de métal du groupe VIII. Selon une deuxième variante de réalisation, le catalyseur mis en oeuvre comprend comme acide fort un hétéropolyacide (i). Cette variante est préférée en raison d'une activité particulièrement avantageuse du catalyseur dans la réaction de sulfhydrolyse.- from 0.01 to 10%, preferably from 0.05 to 1.5% by weight of group VIII metal. According to a second alternative embodiment, the catalyst used comprises, as a strong acid, a heteropolyacid (i). This variant is preferred because of a particularly advantageous activity of the catalyst in the sulfhydrolysis reaction.
La composition catalytique comprend dans ce cas : - de 10 à 60 %, et de préférence de 25 à 50 % en poids d'acide fort,The catalytic composition in this case comprises: from 10 to 60%, and preferably from 25 to 50% by weight of strong acid,
- de 0,01 à 10 %, de préférence de 0,1 à 2 % en poids de métal du groupe VIII, et- from 0.01 to 10%, preferably from 0.1 to 2% by weight of group VIII metal, and
- de 30 à 80 % de préférence de 48 à 75 % en poids d'un support choisi parmi la silice SiO2, l'alumine Al2O3, l'oxyde de titane TiO2, la zircone ZrO2 ou du charbon actif.- from 30 to 80%, preferably from 48 to 75% by weight of a support chosen from silica SiO 2 , alumina Al 2 O 3 , titanium oxide TiO 2 , zirconia ZrO 2 or activated carbon .
Selon un mode de réalisation particulièrement préféré, l'acide fort mis en oeuvre dans le catalyseur est l'acide 12-phosphotungstique, imprégné de préférence sur de la silice. Le ou les métaux appartenant au groupe VIII de la classification périodique généralement compris dans la composition catalytique mise en oeuvre sont choisis parmi notamment le fer, le cobalt, le nickel, le ruthénium, le rhodium, le palladium, l'osmium, l'iridium, le platine. On préfère employer un métal du groupe VIII choisi parmi le palladium, le ruthénium et le platine, et tout particulièrement le palladium.According to a particularly preferred embodiment, the strong acid used in the catalyst is 12-phosphotungstic acid, preferably impregnated on silica. The metal or metals belonging to group VIII of the periodic classification generally included in the catalytic composition used are chosen from in particular iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium , platinum. It is preferred to use a group VIII metal chosen from palladium, ruthenium and platinum, and very particularly palladium.
Une composition catalytique particulièrement préférée est celle comprenant environ : 40 % en poids d'acide 12-phosphotungstique, 1 % de palladium et 59 % de silice. La composition catalytique mise en oeuvre dans le procédé selon l'invention peut être préparée de façon générale de la manière suivante.A particularly preferred catalytic composition is that comprising approximately: 40% by weight of 12-phosphotungstic acid, 1% of palladium and 59% of silica. The catalytic composition used in the process according to the invention can be generally prepared in the following manner.
Lorsque l'acide fort utilisé est l'un des composés (i), on procède à :When the strong acid used is one of the compounds (i), one proceeds to:
- (1) un traitement thermique du support sous vide à une température comprise entre 90 et 150°C, de préférence autour de 100°C, puis - (2) une imprégnation du support ainsi traité avec une solution aqueuse ou organique de pH acide contenant le composé (i) et un précurseur acide du métal du groupe VIII, puis- (1) a heat treatment of the support under vacuum at a temperature between 90 and 150 ° C, preferably around 100 ° C, then - (2) an impregnation of the support thus treated with an aqueous or organic solution of acid pH containing compound (i) and an acid precursor of the group VIII metal, then
- (3) un séchage du solide ainsi obtenu, puis- (3) drying of the solid thus obtained, then
- (4) un traitement par H2 à une température comprise entre 80 et 300°C, de préférence entre 180 et 250 °C.- (4) treatment with H 2 at a temperature between 80 and 300 ° C, preferably between 180 and 250 ° C.
Le traitement thermique de l'étape (1) a pour but de désorber l'eau éventuellement adsorbée dans les pores du support.The purpose of the heat treatment in step (1) is to desorb the water possibly adsorbed in the pores of the support.
Dans l'étape (2), on entend par précurseur acide un composé donnant en solution aqueuse un complexe cationique. ou anionique duditmétal. Des exemples de... tels composés sont, dans le cas du platine : l'hydroxyde de platine tétramine, le chlorure de platine tétramine, le dinitrodiamine-platine (II), ou encore, dans le cas du palladium, le chlorure de palladium, Pd(NH3)4Cl2, (NH4)2(PdCl4). Des exemples de tels composés sont encore, dans le cas du platine : l'acide hexachloroplatinique (encore appelé hexachloroplatinate (IV) d'hydrogène), le tetrachloroplatinate (II) d'ammonium, l'hexachloroplatmate (IV) d'ammonium. La liste des précurseurs acides est donnée précédemment à titre purement illustratif, sans limiter les composés utilisables comme précurseur acide par l'homme du métier.In step (2), the expression “acid precursor” is understood to mean a compound giving an aqueous cationic complex. or anionic of said metal. Examples of ... such compounds are, in the case of platinum: platinum hydroxide tetramine, platinum tetramine chloride, dinitrodiamine-platinum (II), or alternatively, in the case of palladium, palladium chloride , Pd (NH 3 ) 4 Cl 2 , (NH 4 ) 2 (PdCl 4 ). Examples of such compounds are also, in the case of platinum: hexachloroplatinic acid (also called hydrogen hexachloroplatinate (IV)), ammonium tetrachloroplatinate (II), ammonium hexachloroplatinate (IV). The list of acid precursors is given previously for purely illustrative purposes, without limiting the compounds which can be used as acid precursor by those skilled in the art.
Dans l'étape (3), le séchage peut être par exemple réalisé en chauffant le support imprégné, éventuellement sous vide, à une température généralement comprise entre la température ambiante et 120 °C, durant un temps allant de 30 minutes à 5 heures.In step (3), the drying can for example be carried out by heating the impregnated support, optionally under vacuum, to a temperature generally between room temperature and 120 ° C, for a time ranging from 30 minutes to 5 hours.
Le traitement par H2 de l'étape (4) est avantageusement réalisé sur le catalyseur lorsque ce dernier est placé dans le réacteur de sulfhydrolyse, et a pour but la réduction du précurseur acide en métal du groupe VIII.The treatment with H 2 of step (4) is advantageously carried out on the catalyst when the latter is placed in the sulfhydrolysis reactor, and has the aim of reducing the acid precursor to the metal of group VIII.
Lorsque le catalyseur mis en oeuvre comprend comme acide fort un hétéropolyacide (ii), ou l'un des composés (b), (c), (d) ou (e), il peut être préparé selon le même procédé, à l'exception du fait que le traitement thermique n'est pas obligatoire, et doit même être supprimé ou modifié en fonction des caractéristiques du support.When the catalyst used comprises as strong acid a heteropolyacid (ii), or one of the compounds (b), (c), (d) or (e), it can be prepared according to the same process, using except that the heat treatment is not compulsory, and must even be removed or modified according to the characteristics of the support.
La composition catalytique décrite précédemment est mise en oeuvre dans le procédé de fabrication de mercaptan selon l'invention qui comprend la réaction d'hydrogène sulfuré (H2S) sur un thioether en présence d'hydrogène.The catalytic composition described above is used in the process for manufacturing mercaptan according to the invention which comprises the reaction of hydrogen sulfide (H 2 S) on a thioether in the presence of hydrogen.
Ce procédé est effectué en phase gaz, dans la mesure où les conditions de température et de pression utilisées sont telles que les réactifs et les produits sont à l'état gazeux.This process is carried out in the gas phase, insofar as the temperature and pressure conditions used are such that the reactants and the products are in the gaseous state.
L'hydrogène introduit dans le procédé à raison d'une quantité correspondant à un rapport molaire H2S / H2 compris entre 10 et 200, de préférence entre 50 et 100.The hydrogen introduced into the process in an amount corresponding to a H 2 S / H 2 molar ratio of between 10 and 200, preferably between 50 and 100.
Le thioether (ou sulfure organique) utilisé comme réactif de départ a pour formule générale :The thioether (or organic sulfide) used as starting reagent has the general formula:
R-S-R' (I) dans laquelle R et R', identiques ou différents, représentent un radical alkyle de 1 à 20 atomes de carbone, de préférence de 1 à 12 atomes de carbone, linéaire ou ramifié, ou bien un radical cycloalkyle de .3 à 7 atomes de carbone.. " ' On préfère utiliser comme thioether de départ un composé de formule (I) dans laquelle R et R' sont identiques. Dans ce cas en effet, il n'est pas nécessaire de procéder à une séparation des thiols obtenus.RSR '(I) in which R and R', identical or different, represent an alkyl radical of 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, linear or branched, or else a cycloalkyl radical of .3 with 7 carbon atoms. "" It is preferred to use as starting thioether a compound of formula (I) in which R and R 'are identical. In this case in fact, it is not necessary to carry out a separation of the thiols obtained.
Le thioether encore plus préférentiellement utilisé est le diéthylsulfure (ou éthylthioéther). La réaction de sulfhydrolyse conduit dans ce cas à l'éthylmercaptan (ou éthanethiol).The thioether even more preferably used is diethylsulfide (or ethylthioether). The sulfhydrolysis reaction leads in this case to ethylmercaptan (or ethanethiol).
L'hydrogène sulfuré est introduit dans le procédé en quantité suffisante pour obtenir la conversion du sulfure organique. En général cette quantité correspond à un rapport molaire H2S / thioether compris entre 1 et 40, de préférence entre 2 et 30, encore plus préférentiellement entre 2 et 10. Les réactifs décrits ci-dessus sont mis en contact, en présence d'une charge de la composition catalytique définie précédemment, dans une zone réactionnelle adaptée, dans des condtions réactionnelles propres à produire le thiol désiré.The hydrogen sulfide is introduced into the process in an amount sufficient to obtain the conversion of the organic sulfide. In general, this quantity corresponds to a H 2 S / thioether molar ratio of between 1 and 40, preferably between 2 and 30, even more preferably between 2 and 10. The reagents described above are brought into contact, in the presence of a charge of the catalytic composition defined above, in a suitable reaction zone, under reaction conditions suitable for producing the desired thiol.
On préfère mettre en oeuvre le procédé dans un réacteur alimenté en continu par les réactifs, mais un réacteur de type batch peut également être utilisé.It is preferred to carry out the process in a reactor fed continuously with the reactants, but a batch type reactor can also be used.
La température de réaction varie selon le thioether utilisé et le degré de conversion désiré, mais se situe généralement dans un domaine compris entre 50 et 350°C, de préférence entre 150 et 250°C.The reaction temperature varies depending on the thioether used and the degree of conversion desired, but is generally within a range of between 50 and 350 ° C, preferably between 150 and 250 ° C.
La pression à laquelle la réaction est réalisée varie également dans de larges limites. Habituellement, elle se situe entre la pression atmosphérique et 20 bars, de préférence entre 10 et 15 bars.The pressure at which the reaction is carried out also varies within wide limits. Usually, it is between atmospheric pressure and 20 bars, preferably between 10 and 15 bars.
Le temps de contact est généralement compris entre 1 et 50 s, de préférence entre 10 et 30 s.The contact time is generally between 1 and 50 s, preferably between 10 and 30 s.
Le thioether mis en oeuvre dans le procédé selon l'invention peut être le sous- produit obtenu dans un procédé de fabrication de thiol par addition de sulfure d'hydrogène sur un alcool ou sur une oléfine, en présence d'un catalyseur et/ou par activation photochimique. Dans cette variante de procédé, on peut ainsi valoriser avantageusement ledit sous-produit.The thioether used in the process according to the invention may be the by-product obtained in a process for the manufacture of thiol by the addition of hydrogen sulfide on an alcohol or on an olefin, in the presence of a catalyst and / or by photochemical activation. In this variant of the process, it is thus possible to advantageously develop said by-product.
Les exemples ci-après sont donnés à titre purement illustratifs de l'invention, et ne doivent nullement être interprêtés comme une limitation de celle-ci. Dans ces exemples l'abréviation HPW correspond à l'acide 12-phosphotungstique de formule H3PWι2O40,nH2O.The examples below are given purely by way of illustration of the invention, and should in no way be interpreted as a limitation thereof. In these examples the abbreviation HPW corresponds to 12-phosphotungstic acid of formula H 3 PWι 2 O 40 , nH 2 O.
Exemple 1 : Préparation du catalyseur Pd et HPW supportés sur SiO: 2Example 1: Preparation of the catalyst Pd and HPW supported on SiO : 2
Pour 200 g de SiO2, on prépare une solution aqueuse comprenant 6 g de PdCl2 et 140 g d'HPW (poids exprimé en équivalent acide anhydre, soit avec n égal à 0).For 200 g of SiO 2 , an aqueous solution is prepared comprising 6 g of PdCl 2 and 140 g of HPW (weight expressed in anhydrous acid equivalent, ie with n equal to 0).
On utilise comme support du catalyseur une silice amorphe ayant une surface spécifique (ou BET) de 315 un diamètre de pores de l'ordre de 12 à 14 nm et un volume poreux de 1,6 cm .g" . Ce support est préalablement traité sous vide à une température de 100°C. L'imprégnation de la solution précédemment obtenue sur le support ainsi traité est réalisée sous vide par aspiration. Une fois la solution imprégnée, le mélange est agité pendant 1 heure à pression atmosphérique.An amorphous silica having a specific surface (or BET) of 315 is used as catalyst support a pore diameter of the order of 12 to 14 nm and a pore volume of 1.6 cm. g " . This support is previously treated under vacuum at a temperature of 100 ° C. The impregnation of the solution previously obtained on the support thus treated is carried out under vacuum by suction. Once the solution has been impregnated, the mixture is stirred for 1 hour at atmospheric pressure.
Le produit obtenu est séché sous vide, à température ambiante, puis est soumis à un traitement par de l'hydrogène à une température de 230°C visant à réduire le palladium.The product obtained is dried under vacuum, at ambient temperature, then is subjected to a treatment with hydrogen at a temperature of 230 ° C. aimed at reducing the palladium.
Le catalyseur obtenu est constitué de 59% en poids de SiO2, 1% en poids de Pd et 40% en poids d'HPW.The catalyst obtained consists of 59% by weight of SiO 2 , 1% by weight of Pd and 40% by weight of HPW.
Exemple 2 : Préparation de l'éthyl mercaptan (CH3CH2-SH) à partir du diéthylsulfure (CH3CH2-S-CH2CH3) :Example 2: Preparation of ethyl mercaptan (CH 3 CH 2 -SH) from diethyl sulfide (CH 3 CH 2 -S-CH 2 CH 3 ):
On utilise un réacteur tubulaire de 25 mm de diamètre présentant une capacité utile de 200 ml chargé de 200 ml de la composition catalytique préparée selon l'exemple 1.A 25 mm diameter tubular reactor using a useful capacity of 200 ml charged with 200 ml of the catalytic composition prepared according to Example 1 is used.
A travers cette charge, on fait passer par heure, 120 g de diéthylsulfure (soit 1 mole),Through this charge, 120 g of diethyl sulfide (i.e. 1 mole) are passed per hour.
210 g d'H2S (soit 5 moles) et 0,8 g d'H2 (soit 0,08 mole).210 g of H 2 S (i.e. 5 moles) and 0.8 g of H 2 (i.e. 0.08 moles).
La pression dans le réacteur est maintenue à 15 bars et la température est fixée àThe pressure in the reactor is maintained at 15 bars and the temperature is fixed at
235°C. L'analyse en continu des produits bruts de la réaction montre que la conversion initiale du thioether est de 52% avec un rendement en éthyl mercaptan de 49,3%.235 ° C. Continuous analysis of the crude reaction products shows that the initial conversion of thioether is 52% with a yield of ethyl mercaptan of 49.3%.
Exemple 3 : Préparation de l'éthyl mercaptan (CH3CH2-SH) à partir du diéthylsulfure (CH3CH2-S-CH2CH3) - Evolution de la conversion de l'éthyl mercaptan en fonction du temps :Example 3 Preparation of ethyl mercaptan (CH 3 CH 2 -SH) from diethyl sulfide (CH 3 CH 2 -S-CH 2 CH 3 ) - Evolution of the conversion of ethyl mercaptan as a function of time:
On répète l'exemple 2 en poursuivant la réaction de sulfhydrolyse pendant 6 jours avec la même charge de composition catalytique, et en procédant périodiquement (en fonction du temps exprimé en jours) à la mesure de la conversion du diéthyl sulfure (DES).Example 2 is repeated, continuing the sulfhydrolysis reaction for 6 days with the same charge of catalytic composition, and proceeding periodically (as a function of the time expressed in days) to measure the conversion of diethyl sulfide (DES).
Les résultats sont rassemblés dans le tableau suivant. Tableau 1The results are collated in the following table. Table 1
Le tableau 1 montre que le système catalytique préparé à l'exemple 1 et utilisé en présence d'hydrogène selon le procédé de l'invention a une bonne stabilité au cours du temps. Table 1 shows that the catalytic system prepared in Example 1 and used in the presence of hydrogen according to the process of the invention has good stability over time.

Claims

REVENDICATIONS
1. Procédé de fabrication d'un mercaptan à partir d'un thioether et d'hydrogène sulfuré, caractérisé en ce qu'il est effectué en présence d'hydrogène et d'une composition catalytique comprenant un acide fort et au moins un métal appartenant au groupe VIII de la classification périodique.1. A method of manufacturing a mercaptan from a thioether and hydrogen sulfide, characterized in that it is carried out in the presence of hydrogen and a catalytic composition comprising a strong acid and at least one metal belonging in group VIII of the periodic table.
2. Procédé selon la revendication 1, caractérisé en ce que l'acide fort est pris dans le groupe comprenant :2. Method according to claim 1, characterized in that the strong acid is taken from the group comprising:
- (a) un ou plusieurs hétéropolyacide(s) choisi(s) parmi :- (a) one or more heteropolyacid (s) chosen from:
- (i) un composé de formules : H3PWι2O4o,nH2O, H^iW^O^n^O ou H^W^O^n^O dans lesquelles n est un nombre entier représentant le nombre de molécules d'eau de cristallisation, et est compris entre 0 et 30, de préférence entre 6 et 20 ;- (i) a compound of formulas: H 3 PWι 2 O 4 o, nH 2 O, H ^ iW ^ O ^ n ^ O or H ^ W ^ O ^ n ^ O in which n is an integer representing the number molecules of water of crystallization, and is between 0 and 30, preferably between 6 and 20;
- (ii) un sel de potassium, rubidium, césium ou d'ammonium d'au moins un composé (i) ou un mélange de tels sels ;- (ii) a potassium, rubidium, cesium or ammonium salt of at least one compound (i) or a mixture of such salts;
- (b) une zircone sulfatée,- (b) a sulfated zirconia,
- (c) une zircone tungstée, - (d) une zéolithe, et- (c) a tungsten zirconia, - (d) a zeolite, and
- (e) une résine cationique.- (e) a cationic resin.
3. Procédé selon la revendication 2, caractérisé en ce que le catalyseur mis en oeuvre comprend comme acide fort un hétéropolyacide (ii), ou l'un des composés (b), (c), (d) ou (e).3. Method according to claim 2, characterized in that the catalyst used comprises as strong acid a heteropolyacid (ii), or one of the compounds (b), (c), (d) or (e).
4. Procédé selon la revendication 3, caractérisé en ce que la composition catalytique comprend :4. Method according to claim 3, characterized in that the catalytic composition comprises:
- de 90 à 99,9 %, de préférence de 98,5 à 99,5 %, en poids d'acide fort, etfrom 90 to 99.9%, preferably from 98.5 to 99.5%, by weight of strong acid, and
- de 0,01 à 10 %, de préférence de 0,05 à 1,5 % en poids de métal du groupe VIII. - from 0.01 to 10%, preferably from 0.05 to 1.5% by weight of group VIII metal.
5. Procédé selon la revendication 2, catactérisé en ce que le catalyseur mis en oeuvre comprend comme acide fort un hétéropolyacide (i).5. Method according to claim 2, characterized in that the catalyst used comprises as strong acid a heteropolyacid (i).
6. Procédé selon la revendication 5, catactérisé en ce que la composition catalytique comprend :6. Method according to claim 5, characterized in that the catalytic composition comprises:
- de 10 à 60 %, et de préférence de 25 à 50 % en poids d'acide fort,- from 10 to 60%, and preferably from 25 to 50% by weight of strong acid,
- de 0,01 à 10 %, de préférence de 0,1 à 2 % en poids de métal du groupe VIII, et- from 0.01 to 10%, preferably from 0.1 to 2% by weight of group VIII metal, and
- de 30 à 80 % de préférence de 48 à 75 % en poids d'un support choisi parmi la silice SiO2, l'alumine Al2O3, l'oxyde de titane TiO2, la zircone ZrO2 ou du charbon actif.- from 30 to 80%, preferably from 48 to 75% by weight of a support chosen from silica SiO 2 , alumina Al 2 O 3 , titanium oxide TiO 2 , zirconia ZrO 2 or activated carbon .
7. Procédé selon l'une des revendications 5 ou 6, caractérisé en ce que l'acide fort mis en oeuvre dans le catalyseur est l'acide 12-phosphotungstique, imprégné de préférence sur de la silice.7. Method according to one of claims 5 or 6, characterized in that the strong acid used in the catalyst is 12-phosphotungstic acid, preferably impregnated on silica.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le ou les métaux appartenant au groupe VIII de la classification périodique sont choisis parmi le fer, le cobalt, le nickel, le ruthénium, le rhodium, le palladium, l'osmium, l'iridium, le platine.8. Method according to one of claims 1 to 7, characterized in that the metal or metals belonging to group VIII of the periodic table are chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum.
9. Procédé selon la revendication 8, caractérisé en ce que le ou les métaux sont choisis parmi le palladium, le ruthénium et le platine.9. Method according to claim 8, characterized in that the metal or metals are chosen from palladium, ruthenium and platinum.
10. Procédé selon l'une des revendications 8 ou 9, caractérisé en ce que le métal est le palladium.10. Method according to one of claims 8 or 9, characterized in that the metal is palladium.
11. Procédé selon l'une des revendications 1 ou 5 à 10, caractérisé en ce que la composition catalytique comprend environ : 40 % en poids d'acide 12- phosphotungstique, 1 % de palladium et 59 % de silice.11. Method according to one of claims 1 or 5 to 10, characterized in that the catalytic composition comprises approximately: 40% by weight of 12-phosphotungstic acid, 1% of palladium and 59% of silica.
12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que l'hydrogène est introduit à raison d'une quantité correspondant à un rapport molaire H S / H2 compris entre 10 et 200, de préférence entre 50 et 100. 12. Method according to one of claims 1 to 11, characterized in that the hydrogen is introduced in an amount corresponding to a molar ratio HS / H 2 of between 10 and 200, preferably between 50 and 100.
13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce que le thioether utilisé a pour formule générale :13. Method according to one of claims 1 to 12, characterized in that the thioether used has the general formula:
R-S-R' (I) dans laquelle R et R', identiques ou différents, représentent un radical alkyle de 1 à 20 atomes de carbone, de préférence de 1 à 12 atomes de carbone, linéaire ou ramifié, ou bien un radical cycloalkyle de 3 à 7 atomes de carbone.RSR '(I) in which R and R', identical or different, represent an alkyl radical of 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, linear or branched, or else a cycloalkyl radical of 3 to 7 carbon atoms.
14. Procédé selon l'une des revendications 1 à 13, caractérisé en ce que l'hydrogène sulfuré est introduit dans une quantité correspondant à un rapport molaire H2S / thioether compris entre 1 et 40, de préférence entre 2 et 30, encore plus préférentiellement entre 2 et 10. 14. Method according to one of claims 1 to 13, characterized in that the hydrogen sulphide is introduced in an amount corresponding to a H 2 S / thioether molar ratio between 1 and 40, preferably between 2 and 30, again more preferably between 2 and 10.
EP03773807A 2002-09-25 2003-09-23 Catalytic method of producing mercaptans from thioethers Expired - Lifetime EP1542795B1 (en)

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CN1694761A (en) 2005-11-09
CN1694761B (en) 2010-04-28
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JP2006500417A (en) 2006-01-05
WO2004029022A2 (en) 2004-04-08
AU2003282187A8 (en) 2004-04-19
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CA2499632C (en) 2008-08-19
US20060025633A1 (en) 2006-02-02
KR100653588B1 (en) 2006-12-05
EP1542795B1 (en) 2007-02-14
CA2499632A1 (en) 2004-04-08
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